US4049636A - Thermally stable polyurethane elastomer useful in molding flexible automobile exterior body parts - Google Patents

Thermally stable polyurethane elastomer useful in molding flexible automobile exterior body parts Download PDF

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US4049636A
US4049636A US05/661,212 US66121276A US4049636A US 4049636 A US4049636 A US 4049636A US 66121276 A US66121276 A US 66121276A US 4049636 A US4049636 A US 4049636A
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poly
oxypropylene
oxyethylene
glycol
weight
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US05/661,212
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Chung-Ling Mao
Francis X. O'Shea
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Uniroyal Chemical Co Inc
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Uniroyal Inc
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Priority to US05/661,212 priority Critical patent/US4049636A/en
Priority to CA266,291A priority patent/CA1080883A/en
Priority to DD7700197518A priority patent/DD131563A5/xx
Priority to FR7705435A priority patent/FR2342310A1/fr
Priority to AU22613/77A priority patent/AU504503B2/en
Priority to BE175228A priority patent/BE851785A/xx
Priority to DE2708267A priority patent/DE2708267C2/de
Priority to BR7701154A priority patent/BR7701154A/pt
Priority to JP2014177A priority patent/JPS52110799A/ja
Priority to GB8138/77A priority patent/GB1550098A/en
Priority to SE7702120A priority patent/SE7702120L/xx
Priority to AR266691A priority patent/AR216646A1/es
Priority to NLAANVRAGE7702092,A priority patent/NL168855C/xx
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Assigned to UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY reassignment UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NEW YORK CORP.
Assigned to UNIROYAL CHEMICAL COMPANY, INC. reassignment UNIROYAL CHEMICAL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NJ CORP.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6552—Compounds of group C08G18/63
    • C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6564—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/906—Fiber or elastomer prepared from an isocyanate reactant

Definitions

  • Flexible exterior body parts for automobiles including parts associated with energy-absorbing bumper system such as sight shields, fender extensions and full fascia front and rear ends, require a material with a particular set of properties.
  • the material must be capable of flexing under impact and then returning to its original shape. Therefore, it must be elastomeric in nature. It must have strength as typified by high tensile strength and high tear strength.
  • Polyurethane elastomers are "block” type polymers resulting from the reaction of a polymeric diol of molecular weight of from about 500 to 5000 with a diisocyanate and a low molecular weight difunctional compound commonly referred to as the "chain extender".
  • the chain extender has a molecular weight below 500 and generally below 300.
  • the polymeric diol is recognized as the "soft" segment of the elastomer, conferring elasticity and softness to the polymer.
  • this component has a molecular weight of about 1000 to 2000 and may be a poly(alkylene ether) glycol such as poly(tetramethylene ether) glycol or poly(oxypropylene) glycol, a polyester diol, a polycaprolactone diol or polybutadiene diol.
  • polymeric diols recently described for use in polyurethane elastomers are "graft" polyols prepared by the in situ polymerization of ethylenically unsaturated monomers in a polyol. These products are described in U.S. Pat. No. 3,383,351 to Stamberger, May 14, 1968.
  • suitable polyols described are poly(oxypropylene) glycols and mixed poly(oxyethylene)-poly(oxypropylene) glycols (column 8, lines 28-30).
  • Other representative patents describing the preparation of grafted polymer polyols and the polyurethanes made from these polyols are as follows:
  • U.S. Pat. No. 3,523,093, Aug. 4, 1970, Stamberger discloses a method for the preparation of polyurethanes.
  • a mixture comprising a liquid polyol and a preformed normally solid, film-forming polymeric material is reacted with an organic polyisocyanate to form polyurethane foams.
  • thermoplastic polyurethanes based on styrene-acrylonitrile grafted poly(oxypropylene) glycols containing from 0 to about 15% by weight oxyethylene groups is their thermal instability at the elevated processing temperatures used for fabricating urethanes made from such polyols of molecular weight 2000 or greater.
  • polyurethane elastomers as a class have excellent tear strength and tensile strength and can be designed to achieve the required modulus and elongation
  • polyurethane elastomers can meet the two requirements of low temperature impact resistance and resistance to heat distortion.
  • a polyurethane elastomer based on poly(oxypropylene) glycol as the polymeric diol and 1,4-butanediol as the chain extender has not yet been used for flexible automobile body parts because of previous deficiencies of such an elastomer in these two areas. It is generally recognized (N.E. Rustad and R. G. Krawiec, Rubber Age, November 1973, pp.
  • thermoplastic polyurethanes based on an approximately 2000 M n diol are more desirable since they show less modulus-temperature dependence in the use region.” They also concluded: "Apparently at similar hard segment concentrations, the molecular weight of the urethane polymer soft segment has a greater effect on the temperature dependence of physical properties than the hard segment sequences.” They attributed the unique properties of these materials to be the result of incompatibility on a microscopic scale between the hard and soft segments. In turn, “Incompatibility quite probably is due to the molecular weight of the soft segment being high enough to be immiscible in a thermodynamic sense with the hard segment.”
  • polyurethane elastomers suitable for the preparation of flexible automobile exterior body parts may be obtained from the reaction of a mixture comprising:
  • polymeric diol selected from the group consisting of poly(oxypropylene) glycol and ethylene oxide "tipped" poly(oxypropylene) glycol containing up to 10% by weight ethylene oxide and of molecular weight from about 1750 to about 2500 (preferably about 2000);
  • this improvement extends to polymers based on blends of (a) poly(oxypropylene)-poly(oxyethylene) glycols of oxyethylene group content 15% or more in admixture with (b) "graft" polyols prepared by the in situ polymerization of one or more ethylenically unsaturated monomers in a poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol containing less than 15% by weight oxyethylene groups.
  • Preferred (a) glycols are those of molecular weight 1500 to about 4000 and containing 15 to 50% oxyethylene groups by weight.
  • Particularly preferred (a) glycols are poly(oxypropylene)poly(oxyethylene) glycols containing 25 to 50% oxyethylene group content.
  • Such mixed polyol based polymers provide additional surprising advantages in that the resultant elastomers possess improved processability and moldability, largely as a consequence of the fact that they have unexpectedly higher modulus and are harder at elevated temperatures than previously proposed compositions. These unexpected improvements can be important in allowing the molding of parts more economically through the use of shorter cycles.
  • Polyurethane elastomers suitable for the preparation of flexible automobile exterior body parts may be obtained from the reaction of a mixture comprising:
  • a poly(oxypropylene)-poly(oxyethylene) glycol of molecular weight from about 1500 to about 4000 and containing 15% to 50% oxyethylene group content by weight;
  • a "graft" polyol of molecular weight from about 2500 to about 4500 prepared by the in situ polymerization of one or more ethylenically unsaturated monomers in a poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol containing less than 15% by weight oxyethylene groups;
  • typical elastomers of the invention retain at least twice as much of their original tensile strength as similar elastomers in which (a) is omitted or (a) is a poly(oxypropylene)-poly(oxyethylene) glycol containing 10% or less of oxyethylene group content.
  • the elastomers of the invention meet the requirements for flexible exterior body parts for automobiles. They have a hardness of about 40 to 55 Shore D, preferably 45 to 50 Shore D. They have an elongation greater than 300%, an ultimate tensile strength of about 3000 psi or greater and a Die C tear strength of 500 pli or greater.
  • the unit consists basically of a vertical guide tube, a drop weight of appropriate design and associated instrumentation.
  • Polymers to be evaluated were molded into 2 inches ⁇ 6 inches ⁇ 0.08 inch specimens which were conditioned in an evironmental chamber to -20° F. and then fitted into two slots 3 inches apart so that the sample formed an inverted "U" with a total flexed height of 2 inches.
  • the sample was impacted at its center line with a force of 50 ft. lbs., the weight traveling at greater than 5 MPH at impact. Drop height above the top of the sample was 38 inches.
  • the drop weight is an 18 inch long cylinder weighing 16 lbs. It is 2.5 inches in diameter for 16.5 inches of its length and then tapers to a blunt end, which is the striking surface.
  • Parts made from the present elastomers also withstand paint oven temperatures of 250° F. without objectionable shrinkage or distortion.
  • a sag resistance test (Heat Test O'S) was developed.
  • the apparatus consists of a jig to hold a 2 inch ⁇ 6 inch ⁇ 0.08 inch injection molded sample in a horizontal plane. The sample is mounted with 4 inches suspended beyond the edge of the clamp. The jig with the sample is then placed in an oven pre-heated at 250° F. for 1/2 hour. The amount of sag is the difference in height from the end of the sample to a horizontal plane before and after exposure to heat.
  • the poly(oxypropylene)-poly(oxyethylene) glycol (a) used in the invention may be either a "tipped" polyol in which a poly(oxypropylene) glycol is reacted further with ethylene oxide giving rise to oxyethylene group blocks on each end of the polyol or a more random poly(oxypropylene)-poly(oxyethylene) glycol in which the propylene oxide and ethylene oxide reactants are introduced together or in alternating portions.
  • the preparation of both types of polyol is described in "Polyurethanes: Chemistry and Technology", Part I. Chemistry, by J. H.. Saunders and K. C. Frisch, Interscience, New York, 1962, pp. 36-37.
  • the oxyethylene group content of the polyol (a) may range from 15% to 50%, preferably 25-50%, with the higher levels being preferred for the higher molecular weight polyols. For a 2000 molecular weight polyol the preferred oxyethylene group content is 25-45%.
  • the poly(oxypropylene)-poly(oxyethylene) glycol (a) employed has, as indicated, a molecular weight of from about 1500 to about 4000.
  • the ethylenically unsaturated monomeric materials useful for grafting onto poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol to prepare polyol (b) are well known in the art and include the hydrocarbon monomers such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, alphamethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, and the like; substituted styrenes such as chlorostyrene, 2,5-dichlorostyrene, bromostyrene, flurostyrene, trifluoromethylstyrene, iodostyrene, cyanostyrene, nitrostyren
  • Preferred materials are the vinyl aryl monomers (especially styrene and alpha-methyl styrene), the acrylic nitriles (especially acrylonitrile and methacrylonitrile), and the alkyl alkenoate esters (especially methyl and ethyl acrylate and methacrylate), Reaction conditions and free radical catalysts which may be used in the grafting reaction are described in the above-cited Stamberger patent on column 4, lines 15-50.
  • the amounts of polymerized monomer in the graft polyol (b) may range from 5 to 50% by weight as described in the above patent on column 10, lines 2-3.
  • the preferable concentration is about 10% to 30%.
  • the molecular weight of the poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol on which the monomer is grafted to make polyol (b) will vary from 2000 to 4000 with a preferred molecular weight of about 2500 to about 3000.
  • the glycol employed in making the graft (b) is selected from (i) poly(oxypropylene) glycol, (ii) poly(oxypropylene)-poly(oxyethylene) glycol containing up to 15% oxyethylene groups, introduced either randomly or by "tipping" as described above, or (iii) a mixture of (i) and (ii) in any desired proportions (e.g., 90:10, 50:50, 10:90 etc.)
  • the ratio of (a) poly(oxypropylene)-poly(oxyethylene) glycol to (b) ethylenic monomer grafted polyol employed in the invention will range from about 10/90 to 90/10 by weight, with a preferred ratio of from about 80/20 to 40/60.
  • the molar ratio of chain extender (d) to polyol [(a) plus (b)] which may be used depends on the average molecular weight of the polyol mixture and is usually from 6 to 1 to 12 to 1. It ranges from 6 to 1 for a 2500 average molecular weight polyol mixture to 12 to 1 for a 4000 molecular weight polyol mixture.
  • the molar ratio of chain extender (d) to polyol for a 2800 average molecular weight polyol mixture ranges from 5 to 1 to about 9 to 1 with 6.0 to 8.0 being preferred.
  • the NCO/OH ratio used to prepare the flexible thermoplastics may range from 0.95 to 1.10 with 1.00 to 1.05 being preferred.
  • a catalyst may or may not be used as desired.
  • Some examples of useful catalysts are N-methyl-morpholine, N-ethyl-morpholine, triethyl amine, triethylene diamine (Dabco), N,N'-bis(2-hydroxylpropyl)-2-methyl piperazine, dimethyl ethanol amine, tertiary amino alcohols, tertiary ester amines, stannous octoate, dibutyl tin dilaurate and the like.
  • Polyurethane thermoplastics of this invention can be prepared utilizing either prepolymer or one-shot (masterbatch) technique.
  • the prepolymer is formed by reacting an organic polyhydroxyl compound which is a mixture of (a) a poly(oxypropylene) poly-(oxyethylene) glycol and (b) an ethylenic monomer graft on poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol with an organic poly-isocyanate, e.g., methylenebis(phenylisocyanate) to form an isocyanate terminated prepolymer.
  • an organic polyhydroxyl compound which is a mixture of (a) a poly(oxypropylene) poly-(oxyethylene) glycol and (b) an ethylenic monomer graft on poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol
  • an organic poly-isocyanate e.g.,
  • the prepolymer is then treated with an equivalent amount of a low molecular weight polyol chain extender which is 1,4-butanediol and heated at elevated temperatures to effect a "cure".
  • a low molecular weight polyol chain extender which is 1,4-butanediol and heated at elevated temperatures to effect a "cure”.
  • the one-shot or masterbatch system is effected by mixing polyhydroxyl compounds, chain extender and polyisocyanate together simultaneously at moderate temperatures and followed by curing at elevated temperatures.
  • Polyurethanes made from styrene-acrylonitrile grafted poly(oxypropylene) glycol are found to have poor thermal stability (see Example 1, Table II). Unfortunately, physical properties of these polyurethanes are inferior after a normal thermal treatment at 400° F. for 20 minutes, and almost completely deteriorated at 430° for 20 minutes.
  • the flexible polyurethane thermoplastics of this invention made from blends of (a) poly(oxypropylene)-poly(oxyethylene) glycol and (b) ethylenic monomer grafted poly(oxypropylene) and/or poly(oxypropylene)-poly(oxyethylene) glycol exhibit a surprisingly unique combination of properties which neither (a) poly(oxypropylene)-poly(oxyethylene) glycol nor grafted polyol based polyurethane possess.
  • Flexible polyurethane thermoplastics of this invention possess a unique combination of properties such as high tensile strength, high tear resistance, high elongation, good high temperature stability and low temperature flexibility, high resiliency, excellent processability, good moldability and paintability and the raw materials are low in cost. Flexible polyurethane thermoplastics of this invention may be smoothly processed and may easily be molded into large complex articles.
  • thermoplastic elastomers one from a 2000 molecular weight polyol containing 45% by weight ethylene oxide, one from a 3500 molecular weight grafted polyol containing about 10% by weight each of styrene and acrylonitrile and five from the mixture of above two polyols were prepared in the following manner.
  • the ratio equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/5.5/6.5.
  • the ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/6/7.
  • Elastomer A was used for preparing Elastomer C, 280 parts of a 2000 molecular weight poly(oxypropylene) glycol containing 45% by weight of ethylene oxide and 210 parts of a 3500 molecular weight poly(oxypropylene)-poly(oxyethylene) glycol containing about 12% by weight oxyethylene group grafted with about 10% by weight each of styrene and acrylonitrile (Niax 24-32) were mixed together and dried.
  • the polyol mixture then was allowed to react with 400 parts of 4,4'-methylenebis(phenyl isocyanate) under nitrogen atmosphere to form an isocyanate-terminated prepolymer.
  • To 900 parts of the prepolymer at 230° F. was added 123 parts of 1,4-butanediol.
  • the polymer was cured at 325° F. for 20 minutes.
  • the ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1
  • the resultant polymers (A, B and C) were then diced, dried for 2 hours at 230° F. and injection molded into either 2 ⁇ 0.125 ⁇ 0.125 inch tensile bars in a four cavity mold or 3 ⁇ 4 ⁇ 0.08 inch plaques using a 1/2 oz. Newbury injection molding machine at barrel and nozzle temperature of 400° F. to 430° F.
  • the thermal stability test the polymer sample was allowed to stand in the barrel of the machine for 20 minutes at temperature. Physical properties were measured on samples molded with and without this thermal treatment. Properties of Elastomers A, B and C are summarized in Table I and the thermal stability of Elastomers A, B and C are presented in Table II in terms of stress-strain properties.
  • Elastomer A was heat treated at 400° F. for 20 minutes. This polymer had very low viscosity at 430° F.
  • Elastomer B was heat treated at 400° F. for 20 minutes. This polymer was found to be completely degraded at 430° F. for 20 minutes. No sample could be molded.
  • Elastomer C was heat treated at 430° F. for 20 minutes.
  • a polyol mixture of 130 parts of a 1510 molecular weight poly(oxypropylene) glycol containing 15% ethylene oxide and 130 parts of the styrene-acrylonitrile grafted polyol (as described in Example I) was allowed to react with 216 parts of 4,4'-methylenebis-(phenyl isocyanate) to form an isocyanate-terminated prepolymer. 470 parts of the prepolymer then was cured with 65 parts of 1,4-butanediol. The ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/6/7. Physical properties of the elastomer were as follows:
  • Example I Example I (Elastomer C)
  • a mixture of 130 parts of 1800 molecular weight poly(oxypropylene) glycol tipped with 30% by weight of ethylene oxide and 130 parts of a 3500 molecular weight polyol grafted with 10% by weight each of styrene and acrylonitrile (Niax 24-32) was allowed to react with 222 parts of 4,4'-methylenebis(phenyl isocyanate).
  • To 475 parts of the prepolymer was added 67.3 parts of 1,4-butanediol.
  • the polymer was cured at 325° F. for 20 minutes.
  • the ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/7/8. Physical properties of the polymer were as follows:
  • the ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/9/10. Physical properties of the elastomer were as follows:
  • This example demonstrates the use of a different ratio of styrene-acrylonitrile graft on poly(oxypropylene)-poly (oxyethylene) glycol for the preparation of polyurethanes of this invention.
  • a mixture of 150 parts of a 2000 molecular weight poly(oxypropylene) glycol containing 45% ethylene oxide and 150 parts of a 3480 molecular weight poly(oxypropylene)-poly(oxyethylene) glycol, containing 12% oxyethylene groups, grafted with 5% of styrene monomer and 15% of acrylonitrile monomer were allowed to react with 207 parts of 4,4'-methylenebis(phenyl isocyanate) to form an isocyanate-terminated prepolymer.
  • This example illustrates the preparation of polyurethanes of this invention using a one-shot or masterbatch technique.
  • the mixture was allowed to mix well for 30 seconds and poured onto an open mold (12 ⁇ 12 ⁇ 0.5 inch) and cured at 325° F. for 20 minutes.
  • the ratio of equivalents of polyol/chain extender/diisocyanate in the final polymer was 1/7/8.
  • the polymer ws processed and injection molded. Physical properties of the polymer are summarized below:
  • the automotive flexible body parts which are a desired end-product of this invention, are fabricated by injection molding using the already prepared polyurethane thermoplastic elastomer as the molding material.
  • the polymer is made into small dice or pellets suitable for feeding into injection molding machines.
  • an automotive part may also be made by extrusion techniques including profile extrusion and sheet extrusion followed by vacuum forming.
  • the automotive part may also be prepared by "Reaction Injection Molding (RIM)" techniques, in which the reactants are rapidly injected into a mold wherein they cure to form the shaped thermoplastic elastomeric article directly.
  • RIM Reaction Injection Molding
  • the polyol, chain extender and diisocyanate may be reacted in one step (one-shot method) or the polyol and diisocyanate may be prereacted to form a prepolymer and then injected along with the chain extender to form the molded articles (prepolymer method).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
US05/661,212 1976-02-25 1976-02-25 Thermally stable polyurethane elastomer useful in molding flexible automobile exterior body parts Expired - Lifetime US4049636A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US05/661,212 US4049636A (en) 1976-02-25 1976-02-25 Thermally stable polyurethane elastomer useful in molding flexible automobile exterior body parts
CA266,291A CA1080883A (en) 1976-02-25 1976-11-22 Thermally stable polyurethane elastomer
DD7700197518A DD131563A5 (de) 1976-02-25 1977-02-23 Thermisch stabile polyurethan-elastomere
AU22613/77A AU504503B2 (en) 1976-02-25 1977-02-24 Polyurethane elastomer
BE175228A BE851785A (fr) 1976-02-25 1977-02-24 Elastomere de polyurethane stable thermiquement
FR7705435A FR2342310A1 (fr) 1976-02-25 1977-02-24 Elastomere de polyurethane stable thermiquement
BR7701154A BR7701154A (pt) 1976-02-25 1977-02-25 Elastomero de poliuretana termicamente estavel e artigo produzido com o mesmo
JP2014177A JPS52110799A (en) 1976-02-25 1977-02-25 Thermally stable polyurethane elastomer
DE2708267A DE2708267C2 (de) 1976-02-25 1977-02-25 Thermisch stabile Polyurethan- Elastomere
GB8138/77A GB1550098A (en) 1976-02-25 1977-02-25 Thermally stable polyurethane elastomer
SE7702120A SE7702120L (sv) 1976-02-25 1977-02-25 Termisk stabil polyuretanelast
AR266691A AR216646A1 (es) 1976-02-25 1977-02-25 Elastomero de poliuretano termicamente estable y articulo moldeado con dicho elastomero
NLAANVRAGE7702092,A NL168855C (nl) 1976-02-25 1977-02-25 Werkwijze voor de bereiding ven een thermisch stabiel polyurethanelastomeer en voorwerp verkregen daaruit.

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Application Number Priority Date Filing Date Title
US05/661,212 US4049636A (en) 1976-02-25 1976-02-25 Thermally stable polyurethane elastomer useful in molding flexible automobile exterior body parts

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US4049636A true US4049636A (en) 1977-09-20

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JP (1) JPS52110799A (OSRAM)
AR (1) AR216646A1 (OSRAM)
AU (1) AU504503B2 (OSRAM)
BE (1) BE851785A (OSRAM)
BR (1) BR7701154A (OSRAM)
CA (1) CA1080883A (OSRAM)
DD (1) DD131563A5 (OSRAM)
DE (1) DE2708267C2 (OSRAM)
FR (1) FR2342310A1 (OSRAM)
GB (1) GB1550098A (OSRAM)
NL (1) NL168855C (OSRAM)
SE (1) SE7702120L (OSRAM)

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EP0007484A1 (en) * 1978-07-05 1980-02-06 The Dow Chemical Company Process for the preparation of a polyurethane from an organic polyisocyanate or polyisothiocyanate and three different active hydrogen atom containing compounds
US4190711A (en) * 1977-09-29 1980-02-26 Union Carbide Corporation Thermoplastic polyether polyurethane elastomers
US4246363A (en) * 1979-06-18 1981-01-20 The Dow Chemical Company Reaction injection molded polyurethanes having particular flexural modulus factors and at least two thermal transition temperatures in a particular range
US4269945A (en) * 1980-01-24 1981-05-26 The Dow Chemical Company Reaction injection molded polyurethanes employing aliphatic amine chain extenders
US4379904A (en) * 1980-11-24 1983-04-12 The Upjohn Company Novel polyurethane product
US4390645A (en) * 1979-11-23 1983-06-28 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom
US4431754A (en) * 1982-03-01 1984-02-14 The Dow Chemical Company Low viscosity polymer polyols via dilution
US4460715A (en) * 1979-11-23 1984-07-17 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes produced therefrom
US4530941A (en) * 1983-01-26 1985-07-23 The Dow Chemical Company Reaction injection molded polyurethanes employing high molecular weight polyols
US4642320A (en) * 1983-11-02 1987-02-10 The Dow Chemical Company Reaction injection molded polyureas employing high molecular weight amine-terminated polyethers
US4804734A (en) * 1987-05-26 1989-02-14 W. R. Grace & Co.-Conn. Polyurethane composition consisting essentially of a polyether diol, a polyether triol, glycerol, and a polyisocyanate
US4859735A (en) * 1988-09-16 1989-08-22 W. R. Grace & Co.-Conn. Castor oil based polyurethane for bridge deckings and related applications
US4877829A (en) * 1988-05-19 1989-10-31 W. R. Grace & Co.-Conn. Liquid coatings for bridge deckings and the like
US20040076787A1 (en) * 2001-01-22 2004-04-22 Miki Shikano Resin composition, sheet obtained thereform, process for producing sheet, and formed object
CN100497428C (zh) * 2003-12-01 2009-06-10 巴斯福股份公司 包含聚合物多元醇的热塑性聚氨酯
US20110262514A1 (en) * 2008-12-05 2011-10-27 Toshiki Origuchi Polyurethane particle and method for producing polyurethane particles

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US4448903A (en) * 1983-07-25 1984-05-15 Mobay Chemical Corporation Novel system for the production of polyurethanes
JPS6086112A (ja) * 1983-10-17 1985-05-15 Toyo Tire & Rubber Co Ltd 耐摩擦、耐摩耗性ポリウレタン樹脂組成物
CN1293020C (zh) * 2004-06-24 2007-01-03 西安交通大学 一种碳化硅发热元件发热部的制备工艺

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US3933937A (en) * 1974-05-15 1976-01-20 Mccord Corporation Molding-grade polyurethane
US3933938A (en) * 1974-05-15 1976-01-20 Mccord Corporation Grafted polyether diol-based thermoplastic urethane elastomer

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US3523093A (en) 1961-11-28 1970-08-04 Paul Stamberger Method of producing polyurethanes by reacting polyisocyanate with a preformed polymer resulting from polymerization of ethylenically unsaturated monomers
GB1022434A (en) 1961-11-28 1966-03-16 Union Carbide Corp Improvements in and relating to polymers
US3304273A (en) 1963-02-06 1967-02-14 Stamberger Paul Method of preparing polyurethanes from liquid, stable, reactive, filmforming polymer/polyol mixtures formed by polymerizing an ethylenically unsaturated monomer in a polyol
BE759006A (fr) 1969-11-20 1971-05-17 Marles Kuhlmann Wyandotte Copolymeres greffes et preparation de polyurethanes
US3823201A (en) 1972-12-04 1974-07-09 Basf Wyandotte Corp Highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom
US3915937A (en) 1974-05-10 1975-10-28 Uniroyal Inc Poly(oxypropylene) glycol based polyurethane elastomers suitable for automotive body parts
GB1505126A (en) * 1974-05-15 1978-03-22 Mccord Corp Thermoplastic polyurethane

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US3933937A (en) * 1974-05-15 1976-01-20 Mccord Corporation Molding-grade polyurethane
US3933938A (en) * 1974-05-15 1976-01-20 Mccord Corporation Grafted polyether diol-based thermoplastic urethane elastomer

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190711A (en) * 1977-09-29 1980-02-26 Union Carbide Corporation Thermoplastic polyether polyurethane elastomers
EP0007484A1 (en) * 1978-07-05 1980-02-06 The Dow Chemical Company Process for the preparation of a polyurethane from an organic polyisocyanate or polyisothiocyanate and three different active hydrogen atom containing compounds
US4246363A (en) * 1979-06-18 1981-01-20 The Dow Chemical Company Reaction injection molded polyurethanes having particular flexural modulus factors and at least two thermal transition temperatures in a particular range
US4390645A (en) * 1979-11-23 1983-06-28 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom
US4460715A (en) * 1979-11-23 1984-07-17 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes produced therefrom
US4269945A (en) * 1980-01-24 1981-05-26 The Dow Chemical Company Reaction injection molded polyurethanes employing aliphatic amine chain extenders
US4379904A (en) * 1980-11-24 1983-04-12 The Upjohn Company Novel polyurethane product
US4431754A (en) * 1982-03-01 1984-02-14 The Dow Chemical Company Low viscosity polymer polyols via dilution
US4530941A (en) * 1983-01-26 1985-07-23 The Dow Chemical Company Reaction injection molded polyurethanes employing high molecular weight polyols
US4642320A (en) * 1983-11-02 1987-02-10 The Dow Chemical Company Reaction injection molded polyureas employing high molecular weight amine-terminated polyethers
US4804734A (en) * 1987-05-26 1989-02-14 W. R. Grace & Co.-Conn. Polyurethane composition consisting essentially of a polyether diol, a polyether triol, glycerol, and a polyisocyanate
US4877829A (en) * 1988-05-19 1989-10-31 W. R. Grace & Co.-Conn. Liquid coatings for bridge deckings and the like
US4859735A (en) * 1988-09-16 1989-08-22 W. R. Grace & Co.-Conn. Castor oil based polyurethane for bridge deckings and related applications
US20040076787A1 (en) * 2001-01-22 2004-04-22 Miki Shikano Resin composition, sheet obtained thereform, process for producing sheet, and formed object
US6998439B2 (en) * 2001-01-22 2006-02-14 Toyo Ink Manufacturing Co., Ltd. Resin composition, sheet obtained therefrom, process for producing sheet, and formed object
CN100497428C (zh) * 2003-12-01 2009-06-10 巴斯福股份公司 包含聚合物多元醇的热塑性聚氨酯
US20110262514A1 (en) * 2008-12-05 2011-10-27 Toshiki Origuchi Polyurethane particle and method for producing polyurethane particles

Also Published As

Publication number Publication date
FR2342310A1 (fr) 1977-09-23
DE2708267C2 (de) 1982-03-11
JPS5414159B2 (OSRAM) 1979-06-05
NL7702092A (nl) 1977-08-29
BR7701154A (pt) 1977-10-18
AR216646A1 (es) 1980-01-15
JPS52110799A (en) 1977-09-17
NL168855C (nl) 1982-05-17
DD131563A5 (de) 1978-07-05
DE2708267A1 (de) 1977-09-08
CA1080883A (en) 1980-07-01
FR2342310B1 (OSRAM) 1981-07-24
BE851785A (fr) 1977-08-24
AU504503B2 (en) 1979-10-18
AU2261377A (en) 1978-08-31
GB1550098A (en) 1979-08-08
SE7702120L (sv) 1977-08-26

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